JP2933220B2 - Polyamide resin-metal laminate - Google Patents

Polyamide resin-metal laminate

Info

Publication number
JP2933220B2
JP2933220B2 JP63067909A JP6790988A JP2933220B2 JP 2933220 B2 JP2933220 B2 JP 2933220B2 JP 63067909 A JP63067909 A JP 63067909A JP 6790988 A JP6790988 A JP 6790988A JP 2933220 B2 JP2933220 B2 JP 2933220B2
Authority
JP
Japan
Prior art keywords
polyamide resin
epoxy resin
spectrum
atomic
metal laminate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP63067909A
Other languages
Japanese (ja)
Other versions
JPH01238931A (en
Inventor
法夫 吉賀
昌寛 河村
寛 野々山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Plastics Inc
Original Assignee
Mitsubishi Plastics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Priority to JP63067909A priority Critical patent/JP2933220B2/en
Priority to US07/409,317 priority patent/US5024891A/en
Priority to EP89117405A priority patent/EP0418414B1/en
Publication of JPH01238931A publication Critical patent/JPH01238931A/en
Application granted granted Critical
Publication of JP2933220B2 publication Critical patent/JP2933220B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2363/00—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2377/00—Polyamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31728—Next to second layer of polyamide
    • Y10T428/31732—At least one layer is nylon type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31739—Nylon type

Landscapes

  • Laminated Bodies (AREA)

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は、ポリアミド樹脂が金属体表面に極めて強固
に結合したポリアミド樹脂−金属積層体に関する。Description: TECHNICAL FIELD The present invention relates to a polyamide resin-metal laminate in which a polyamide resin is very firmly bonded to the surface of a metal body.

〔従来の技術及びその課題） 鋼板やアルミニウム板等の金属素材にポリアミド樹脂
を被覆した金属積層体が、ポリアミド樹脂の有する優れ
た電気絶縁性、耐溶剤性等の特性を生かして種々の分野
で使用されている。[Conventional technology and its problems] A metal laminate, in which a metal material such as a steel plate or an aluminum plate is coated with a polyamide resin, can be used in various fields by taking advantage of the properties of polyamide resin such as excellent electrical insulation and solvent resistance. in use.

このような金属積層体では、層間の接着性が悪いため
金属素材とポリアミド樹脂層間に接着剤を介在させて被
覆することがなされ、接着剤としては、通常、アクリル
樹脂系接着剤、エポキシ樹脂系接着剤、ポリエステル系
接着剤等が使用されている。In such a metal laminate, the adhesiveness between the layers is poor, so that the metal material and the polyamide resin layer are coated with an adhesive interposed therebetween, and the adhesive is usually an acrylic resin-based adhesive, an epoxy resin-based adhesive. Adhesives, polyester-based adhesives and the like are used.

上記接着剤では硬化剤を使用し熱硬化させるために接
着層の剛性が大きくなり、絞り加工や曲げ加工等の二次
加工性に劣る。例えば、金属素材として板状体のものを
使用し、有底状の容器を製造する場合、積層体を多段絞
り等の絞り加工やしごき加工を施すことがなされ、加工
時の接着層に圧縮力、引張力及び剪断力等が作用するた
め、層間剥離が生じやすいという問題があった。本発明
は層間の接着性に優れ、各種の二次加工によっても、層
間剥離しにくいポリアミド樹脂−金属積層体を提供する
ことを目的としている。In the above-mentioned adhesive, the rigidity of the adhesive layer is increased due to the use of a curing agent and thermal curing, and the secondary workability such as drawing or bending is inferior. For example, when manufacturing a container with a bottom using a plate-shaped body as a metal material, the laminate is subjected to drawing such as multi-stage drawing or ironing, and a compressive force is applied to the adhesive layer at the time of processing. In addition, there is a problem that delamination is likely to occur due to a tensile force, a shearing force and the like acting. An object of the present invention is to provide a polyamide resin-metal laminate which has excellent interlayer adhesion and is hardly delaminated even by various types of secondary processing.

（課題を解決するための手段） 上記目的を達成するために本発明のポリアミト樹脂−
金属積層体においては、金属素材表面上に特定の元素構
成からなる熱処理したエポキシ樹脂塗膜を設けたもので
あって、その要旨とするところは、 金属素材にエポキシ樹脂単体の塗膜を0.01〜10μ塗布
し、次いで該塗膜がＸ線光電子分光法（ESCA法）により
測定した表面分析スペクトル値が下記の範囲となるよう
に、処理温度350℃以上で熱処理した後、ポリアミド樹
脂を積層したことを特徴とするポリアミド樹脂−金属積
層体。(Means for Solving the Problems) In order to achieve the above object, the polyamide resin of the present invention is used.
In the metal laminate, a heat-treated epoxy resin coating composed of a specific element composition is provided on the surface of the metal material. 10 μm applied, and then heat-treated at a treatment temperature of 350 ° C. or more so that the coating film has a surface analysis spectrum value measured by X-ray photoelectron spectroscopy (ESCA method) within the following range, and then laminated a polyamide resin. A polyamide resin-metal laminate characterized by the following.

（１）炭素元素（C1sスペクトル部）の相対元素存在比
が、50原子％以上。(1) The relative element abundance ratio of carbon element (C1s spectrum part) is 50 atomic% or more.

（２）C1sスペクトルのＣ＝Ｏ、Ｃ−Ｏ、Ｃ＝Ｃ−Ｃ＝
Ｃ、CH、及びＣ−Ｃの各官能基につき、各波形解析によ
り求めた相対存在比において、Ｃ＝Ｏ基が4.0原子％以
上で、かつＣ−Ｏ基が25原子％以下 にある。(2) C = O, C—O, C = CC of the C1s spectrum
For each of the functional groups C, CH, and CC, the relative abundance determined by each waveform analysis indicates that the C ＝ O group is 4.0 atomic% or more and the CO group is 25 atomic% or less.

本発明に使用する金属素材としては、鋼板、銅板、ス
テンレス板、アルミニウム板等の板状体や棒状、円柱状
等各種形状のものが使用できる。さらに表面をリン酸−
クロム酸塩等による化成処理や電解エッチング等のエッ
チング処理を施した金属素材も使用できる。As the metal material used in the present invention, a plate-like body such as a steel plate, a copper plate, a stainless steel plate, and an aluminum plate, and various shapes such as a rod-like shape and a column-like shape can be used. Further phosphoric acid surface
A metal material subjected to a chemical conversion treatment with chromate or the like or an etching treatment such as electrolytic etching can also be used.

上記金属素材表面には、Ｘ線光電子分光法（ESCA法）
により測定した表面分析スペクトル値が特定範囲の熱処
理したエポキシ樹脂単体の塗膜を設ける必要がある。X-ray photoelectron spectroscopy (ESCA method)
It is necessary to provide a heat-treated epoxy resin coating film having a surface analysis spectrum value measured by the above-mentioned specific range.

ここでＸ線光電子分光法（ESCA法）とは軟質Ｘ線の照
射により試料表面の原子から叩き出された光電子の分光
スペクトルから試料の表面近傍の元素の種類及び化学結
合状態を分析する方法である。Here, X-ray photoelectron spectroscopy (ESCA) is a method of analyzing the types of elements and the chemical bonding state near the surface of a sample from the spectrum of photoelectrons struck out from atoms on the surface of the sample by irradiation with soft X-rays. is there.

熱処理したエポキシ樹脂塗膜のESCA法分析値は下記の
（１）、（２）を満足する必要がある。The analysis value of the heat-treated epoxy resin coating film by the ESCA method must satisfy the following (1) and (2).

（１）炭素元素（C1sスペクトル部）の相対元素存在比
が、50原子％以上。(1) The relative element abundance ratio of carbon element (C1s spectrum part) is 50 atomic% or more.

（２）C1sスペクトルのＣ＝Ｏ、Ｃ−Ｏ、Ｃ＝Ｃ−Ｃ＝
Ｃ、CH、及びＣ−Ｃの各官能基につき、各波形解析によ
り求めた相対存在比において、Ｃ＝Ｏ基が4.0原子％以
上で、かつＣ−Ｏ基が25原子％以下。(2) C = O, C—O, C = CC of the C1s spectrum
In the relative abundances determined by each waveform analysis for each of the functional groups C, CH, and CC, the C ＝ O group is 4.0 atom% or more and the CO group is 25 atom% or less.

ここで上記ESCA法の測定条件は、通常の測定条件でよ
く、例えばＸ線源がMgKαで、出力15KV×33mA、真空度
が５×10-8torrにおいて、C1sスペクトルを結合エネル
ギー296.0eVから282eVまで変化させ、各元素及び各官能
基のスペクトル強度分布から測定したものである。Here, the measurement conditions of the ESCA method may be ordinary measurement conditions, for example, when the X-ray source is MgKα, the output is 15 KV × 33 mA, the degree of vacuum is 5 × 10 −8 torr, and the C1s spectrum is converted from a binding energy of 296.0 eV to 282 eV. And measured from the spectral intensity distribution of each element and each functional group.

上記の１、２を満足するエポキシ樹脂塗膜ではポリア
ミド樹脂との接着が極めて強固である。その理由は明確
には説明できないが、エポキシ樹脂中のエポキシ基の開
環によるＣ−Ｏ基がＣ＝Ｏ基に変性することにより、ポ
リアミド樹脂中のアミド結合 との間で水素結合が起こり、強固な接着力が得られるも
のと推察される。The epoxy resin coating film satisfying the above requirements 1 and 2 has extremely strong adhesion to the polyamide resin. Although the reason cannot be explained clearly, the modification of the C—O group into a C ＝ O group by ring opening of the epoxy group in the epoxy resin leads to an amide bond in the polyamide resin. It is presumed that hydrogen bonding takes place between these and a strong adhesive force is obtained.

本発明で使用するエポキシ樹脂としては、例えば構造
式 で表わされるビスフェノール型エポキシ樹脂、具体的
にはビスフェノールＡモノグリシジルエーテル、ビスフ
ェノールＡジグリシジルエーテルが挙げられる。この他
にビスフェノールＦ型、レゾルシル型エポキシ樹脂等の
各種エポキシ樹脂が使用できる。上記エポキシ樹脂の分
子量は300〜3000程度、エポキシ当量は150〜3200のもの
が好適に使用できる。ここで、上記エポキシ樹脂には通
常の接着剤で使用されている硬化剤は使用しない。硬化
剤の使用は絞り加工や曲げ加工等の二次加工性に劣ると
いう問題がある。As the epoxy resin used in the present invention, for example, the structural formula And specifically, bisphenol A monoglycidyl ether and bisphenol A diglycidyl ether. In addition, various epoxy resins such as bisphenol F type and resorcil type epoxy resin can be used. The epoxy resin having a molecular weight of about 300 to 3000 and an epoxy equivalent of 150 to 3200 can be suitably used. Here, the epoxy resin does not use a curing agent used in a normal adhesive. There is a problem that the use of the curing agent is inferior in secondary workability such as drawing and bending.

上記硬化剤を使用しないエポキシ樹脂（以下、「エポ
キシ樹脂単体」という）は金属素材の表面に塗布し熱処
理する必要がある。塗布する方法としては、金属素材の
形状等により異なるが、例えば板状体の場合、上記エポ
キシ樹脂単体を単独又はメチルエチルケトン、アセト
ン、トルエン、トリクレン、111−トリクロルエタン等
の溶剤で希釈した後、グラビアロール方法、リバースロ
ール方法、キスロール方法、エアーナイフコート方法、
ディップ方法等の通常のコーティング方法により、所定
量を塗布する。It is necessary to apply an epoxy resin that does not use the above curing agent (hereinafter, referred to as "epoxy resin alone") to the surface of a metal material and heat-treat it. The method of application varies depending on the shape and the like of the metal material.For example, in the case of a plate, the epoxy resin alone is used alone or diluted with a solvent such as methyl ethyl ketone, acetone, toluene, trichlene, 111-trichloroethane, and then gravure. Roll method, reverse roll method, kiss roll method, air knife coat method,
A predetermined amount is applied by a usual coating method such as a dip method.

塗布量は使用する金属板の種類等によって異なるが、
乾燥固化後の厚みが0.01μ〜10μ、好ましくは0.02μ〜
７μとなるように塗布する。0.01μ未満では、接着力が
得られず、二次加工時に層間の剥離が生じ易く、同様
に、10μを越すものでも剥離強度の低下がみられ、不都
合である。The amount of application varies depending on the type of metal plate used, etc.
The thickness after drying and solidification is from 0.01 μm to 10 μm, preferably from 0.02 μm
It is applied to be 7 μm. If it is less than 0.01 μm, adhesive strength cannot be obtained, and delamination between layers is likely to occur at the time of secondary processing. Similarly, if it exceeds 10 μm, the peel strength is reduced, which is inconvenient.

塗布されたエポキシ樹脂単体を熱処理することによ
り、上記ESCA法のスペクトル範囲を満足することができ
る。熱処理条件はエポキシ樹脂単体塗布後の金属素材を
処理温度、350℃以上で焼付ければよく、スペクトル値
が上記範囲内になるように適宜条件を決めればよい。The spectrum range of the above ESCA method can be satisfied by heat-treating the applied epoxy resin alone. The heat treatment conditions may be such that the metal material after the application of the epoxy resin alone is baked at a processing temperature of 350 ° C. or higher, and conditions may be appropriately determined so that the spectrum value falls within the above range.

本発明の金属積層体に使用するポリアミド樹脂として
は、６−ナイロン、11−ナイロン、12−ナイロン、66ナ
イロン、610−ナイロン、612−ナイロン及び6/66共重合
ナイロン等が挙げられ、さらにポリアミド系エラストマ
ー、耐衝撃性ポリアミドも使用できる。Examples of the polyamide resin used for the metal laminate of the present invention include 6-nylon, 11-nylon, 12-nylon, 66 nylon, 610-nylon, 612-nylon and 6/66 copolymer nylon, and further polyamide. A series elastomer and an impact-resistant polyamide can also be used.

ポリアミド系エラストマーとしては、６−ナイロン、
66−ナイロン等をハードセグメントとし、ポリエーテ
ル、ポリエステル等をソフトセグメントとしたものであ
る。As polyamide-based elastomers, 6-nylon,
66-nylon and the like are used as hard segments, and polyether and polyester are used as soft segments.

耐衝撃性ポリアミドは66−ナイロン、６−ナイロン樹
脂を主体に変性ポリオレフィン等を溶融ブレンドしたポ
リアミド系ポリマーアロイである。変性ポリオレフィン
としてはエチレン−プロピレン−ジエン共重合体に無水
マレイン酸をグラフトした変性エチレン−プロピレン−
ジエン共重合体やエチレン−メタアクリル酸共重合体を
Na、Zn、Mg等でイオン化したアイオノマー樹脂等が挙げ
られる。The impact-resistant polyamide is a polyamide-based polymer alloy obtained by melt-blending a modified polyolefin or the like mainly with 66-nylon or 6-nylon resin. As the modified polyolefin, modified ethylene-propylene obtained by grafting maleic anhydride onto an ethylene-propylene-diene copolymer is used.
Diene copolymer or ethylene-methacrylic acid copolymer
Examples include ionomer resins ionized with Na, Zn, Mg, and the like.

つぎに、エポキシ樹脂単体塗布面に、上述したポリア
ミド樹脂を積層する。積層方法は金属素材の形状等によ
り異なるが、板状体の場合、コートハンガーダイ、Ｔダ
イ、Ｉダイ等の口金を取付けた押出機により、フイルム
を押出しながら被覆する、いわゆる押出しラミネート方
法や、あらかじめ製膜されたフイルムを用いて、フイル
ムの軟化温度以上に加熱された金属板上にニップロール
で熱圧着する方法等がある。Next, the above-mentioned polyamide resin is laminated on the surface of the single epoxy resin application. The lamination method varies depending on the shape of the metal material and the like, but in the case of a plate-like body, a so-called extrusion lamination method in which a film is extruded and coated with an extruder equipped with a die such as a coat hanger die, a T die, and an I die, There is a method of thermocompression bonding using a nip roll on a metal plate heated to a temperature higher than the softening temperature of the film using a film formed in advance.

上記方法で熱圧着した後、冷却することで所望の積層
体が得られるが、さらにポリアミド樹脂の軟化温度以上
の温度で熱処理することにより剥離強度の向上が図れ
る。A desired laminate is obtained by cooling after thermocompression bonding by the above method, but by further heat-treating at a temperature higher than the softening temperature of the polyamide resin, the peel strength can be improved.

以下、本発明を実施例にて説明する。Hereinafter, the present invention will be described with reference to examples.

（実施例） 実施例 NO.1〜４ 金属素材として、リン酸−クロム酸塩処理液で化成処
理した、厚みが0.4mmのアルミニウム板（1100−H18材）
を用いた。この化成処理したアルミニウム板の片面に分
子量が380で、エポキシ当量が180〜200のビスフェノー
ル型エポキシ樹脂をメチルエチルケトンに溶解した後、
リバースロールコーターで塗布、乾燥した。(Examples) Example Nos. 1 to 4 As a metal material, a 0.4 mm-thick aluminum plate (1100-H18 material) treated with a phosphoric acid-chromate treatment solution
Was used. After dissolving a bisphenol-type epoxy resin having a molecular weight of 380 and an epoxy equivalent of 180 to 200 on one side of this chemically treated aluminum plate in methyl ethyl ketone,
It was applied and dried with a reverse roll coater.

ついで各サンプルを表１に示した250℃以上の熱処理
条件で、表１のスペクトル値を示すように処理したあ
と、６ナイロンフイルム（30μ）をナイロンの融点以上
に加熱した上記アルミニウム板上に積層した。Next, each sample was treated under the heat treatment conditions of 250 ° C. or more shown in Table 1 so as to show the spectrum values shown in Table 1, and then 6 nylon films (30 μ) were laminated on the above aluminum plate heated above the melting point of nylon. did.

ついで、得られた各積層体を用いて、『常態剥離強
度』及び『変形後剥離強度』について評価した結果を表
−１に示した。なお、各項目の評価方法は次の方法で実
施した。Table 1 shows the results of evaluating the “normal peel strength” and the “post-deformation peel strength” using each of the obtained laminates. In addition, the evaluation method of each item was implemented by the following method.

『常態剥離強度』……各アルミニウム積層体（総厚みが
0.50mmの積層体）から、20mm幅の試料を切出し、アルミ
ニウム層にノッチを入れ、180折返して剥離面を作った
後、50mm/minの剥離速度で剥離試験を行ない剥離した時
の荷重を測定した。"Normal peel strength" ... Each aluminum laminate (total thickness
Cut out a 20mm wide sample from the 0.50mm laminate), make a notch in the aluminum layer, turn it 180 times to make a peeled surface, then perform a peel test at a peel speed of 50mm / min and measure the load when peeled did.

『変形後剥離強度』……上記積層体を35mm/minの速度で
20％引張り変形をさせた後、試料を切出し、上記と同様
な剥離試験を行ない剥離した時の荷重を測定した。"Peel strength after deformation" ... The above laminate is processed at a speed of 35 mm / min.
After 20% tensile deformation, the sample was cut out and subjected to the same peeling test as described above to measure the load at the time of peeling.

NO.5 塗布したエポキシ樹脂を熱処理しない他は上記方法と
同一。NO.5 Same as above except that the applied epoxy resin is not heat treated.

NO.6 エポキシ樹脂を介在させないで積層した他は上記方法
と同一。NO.6 Same as above except for laminating without epoxy resin.

表−１から本発明のポリアミド樹脂−金属積層体であ
るNO.1乃至NO.2については層間の接着強度が極めて強固
で、常態及び変形後も剥離不能であることが判る。これ
に対してスペクトル強度が範囲外であるNO.3乃至NO.6に
ついては剥離強度が劣ることが判る。 From Table 1, it can be seen that for the polyamide resin-metal laminates No. 1 and No. 2 of the present invention, the adhesive strength between the layers is extremely strong, and they cannot be peeled off under normal conditions and after deformation. On the other hand, it can be seen that the peel strengths of NO. 3 to NO. 6 whose spectral intensities are out of the range are inferior.

（発明の効果） 上述したように本発明のポリアミド樹脂−金属積層体
は層間の接着力が強固であり、多段の絞り加工やしごき
加工等の各種の二次加工においても層間剥離を生じない
という利点があり、特に絶縁性を要求される電気材料分
野での利用性が大である。(Effects of the Invention) As described above, the polyamide resin-metal laminate of the present invention has a strong adhesive force between layers, and does not cause delamination even in various secondary processes such as multi-stage drawing and ironing. It has advantages, and is particularly useful in the field of electrical materials that require insulation.

フロントページの続き (72)発明者 野々山 寛 滋賀県長浜市三ツ矢町５番８号 三菱樹 脂株式会社長浜工場内 (56)参考文献 特開 昭56−30479（ＪＰ，Ａ)Continuation of the front page (72) Inventor Hiroshi Nonoyama 5-8, Mitsuya-cho, Nagahama-shi, Shiga Prefecture Mitsubishi Plastics Co., Ltd. Nagahama Plant (56) References JP-A-56-30479 (JP, A)

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】金属素材にエポキシ樹脂単体の塗膜を0.01
〜10μ塗布し、次いで該塗膜がＸ線光電子分光法（ESCA
法）により測定した表面分析スペクトル値が下記の範囲
となるように、処理温度350℃以上で熱処理した後、ポ
リアミド樹脂を積層したことを特徴とするポリアミド樹
脂−金属積層体。 （１）炭素元素（C1sスペクトル部）の相対元素存在比
が、50原子％以上。 （２）C1sスペクトルのＣ＝Ｏ、Ｃ−Ｏ、Ｃ＝Ｃ−Ｃ＝
Ｃ、CH、及びＣ−Ｃの各官能基につき、各波形解析によ
り求めた相対存在比において、Ｃ＝Ｏ基が4.0原子％以
上で、かつＣ−Ｏ基が25原子％以下。1. A metal material is coated with a coating film of an epoxy resin alone for 0.01
.About.10 .mu.m and then the coating is applied to X-ray photoelectron spectroscopy (ESCA
A polyamide resin-metal laminate obtained by heat-treating at a treatment temperature of 350 ° C. or higher and then laminating a polyamide resin so that the surface analysis spectrum value measured by the above method falls within the following range. (1) The relative element abundance ratio of carbon element (C1s spectrum part) is 50 atomic% or more. (2) C = O, C—O, C = CC of the C1s spectrum
For the relative abundances determined by waveform analysis for each of the C, CH, and CC functional groups, the C ＝ O group is 4.0 atomic% or more and the CO group is 25 atomic% or less.
JP63067909A 1988-03-22 1988-03-22 Polyamide resin-metal laminate Expired - Lifetime JP2933220B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP63067909A JP2933220B2 (en) 1988-03-22 1988-03-22 Polyamide resin-metal laminate
US07/409,317 US5024891A (en) 1988-03-22 1989-09-19 Polyamide resin-metal laminate
EP89117405A EP0418414B1 (en) 1988-03-22 1989-09-20 Polyamide resin-metal laminate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63067909A JP2933220B2 (en) 1988-03-22 1988-03-22 Polyamide resin-metal laminate

Publications (2)

Publication Number Publication Date
JPH01238931A JPH01238931A (en) 1989-09-25
JP2933220B2 true JP2933220B2 (en) 1999-08-09

Family

ID=13358502

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63067909A Expired - Lifetime JP2933220B2 (en) 1988-03-22 1988-03-22 Polyamide resin-metal laminate

Country Status (3)

Country Link
US (1) US5024891A (en)
EP (1) EP0418414B1 (en)
JP (1) JP2933220B2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11245330A (en) * 1998-03-02 1999-09-14 Toyo Kohan Co Ltd Manufacture of polyamide resin-coated metal plate with excellent processing adhesion, polyamide resin-coated metal plate and container using it
FI19991831A (en) * 1999-08-30 2001-02-28 Upm Kymmene Corp Coating of insulating materials
CN1639387B (en) * 2000-07-31 2012-01-18 三菱树脂株式会社 Aluminum plate with thermoplastic resin coating and formed article comprising the same
WO2020076932A1 (en) 2018-10-09 2020-04-16 Dupont Polymers, Inc. Polymer metal hybrid laminates

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1254048A (en) * 1969-07-12 1971-11-17 Toyo Seikan Kaisha Ltd Primer for metals
JPS556317B2 (en) * 1973-06-20 1980-02-15
GB1500618A (en) * 1974-02-08 1978-02-08 Toa Gosei Chem Ind Coated steel plate suitable for bonding with a polyamide adhesive
US4369222A (en) * 1978-12-22 1983-01-18 Monsanto Company Metal-thermoplastic-metal laminates
JPS5630479A (en) * 1979-08-23 1981-03-27 Ube Ind Ltd Primer for polyamide
US4759972A (en) * 1986-02-26 1988-07-26 Mitsubishi Plastics Industries Limited Aluminum laminate sheet for deep-drawing and aluminum casing for an aluminum electrolytic capacitor

Also Published As

Publication number Publication date
EP0418414B1 (en) 1995-02-22
EP0418414A1 (en) 1991-03-27
JPH01238931A (en) 1989-09-25
US5024891A (en) 1991-06-18

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